Hydroxyamide acid products and butyrolactone and butyrolactam products

ABSTRACT

Metal salts and amides of alkyl-lactam acetic acids are prepared by reacting gamma-hydrocarbyl butyrolactone acetic acid compounds derived from alkenylsuccinic anhydrides with metal compounds and amines or amines alone. High molecular weight lactam acid salts and amides and metal complexes and metal carbamates thereof are useful as detergents or dispersants in organic industrial fluids. Another aspect of this invention is a method of preparing lactone acetic acids in yields up to 90% conversion from alkenylsuccinic anhydrides.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a division of copending application Ser. No. 618,173, filedSept. 30, 1975 now U.S. Pat. No. 4,190,558 which is acontinuation-in-part of U.S. application Ser. No. 355,360, filed Apr.27, 1973, now U.S. Pat. No. 3,925,232 which, in turn, is acontinuation-in-part of U.S. application Ser. No. 212,626, filed Dec.27, 1971, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to metal salts or amides and metal or amidelactones and lactams for use as hard water soaps and organic fluidadditives. In particular, this invention relates to soaps and amides oflactone acetic acids derived from alkenylsuccinic anhydrides.

2. Description of the Prior Art

In an article of D. D. Phillips and A. W. Johnson (Journal of theAmerican Chemical Society, Vol. 77, page 5977, 1955), there is describeda reaction of allylic-substituted succinic anhydride with 6 normalhydrochloric acid. This article does not disclose reaction of thelactone acetic acid with an alkali metal and an amine.

In U.S. Pat. Nos. 3,200,075 and 3,261,782 there are described thepreparations of esters and amides of alkyl butyrolactone acetic acidswhich are obtained by reacting an olefin with di-methyl bromosuccinate.However, the final products of this patent are not the same as thoseprepared in accordance with the present invention.

SUMMARY OF THE INVENTION

We have discovered that organo-substituted lactone acetic acids or theiresters or thioesters derived from alkenylsuccinic anhydrides may bereacted with (a) an alkali metal compound and an amine in either orderor (b) an amine to produce two types of products:

(1) a metal or amine salt or amide of 3-amidocarbonyl- or3-metallocarboxy-5-hydroxycarboxylic acid, and

(2) a metal salt or amide of a butyrolactam acetic acid. The lowermolecular weight carboxylates of Type 1 are extremely effective as hardwater soaps or detergents. The higher molecular weight lactam aceticacid salts or amides of Type 2 or their metal complexes or carbamatesare useful as organic industrial fluid dispersants or detergents.

DESCRIPTION OF SPECIFIC EMBODIMENTS

In accordance with this invention, organo-substituted gamma-lactoneacetic acid may be obtained by subjecting alkenylsuccinic anhydrides toacid hydrolysis. The preparation of the anhydrides is known (U.S. Pat.Nos. 2,568,876 and 3,219,666). Essentially, this preparation involvesthe reaction between a 1-olefin and maleic anhydride (or halosuccinic orsuccinate ester). It is understood that one effect of this reactioninvolves predominantly a shift of the unsaturated bond of the olefin toproduce the alkenylsuccinic anhydride ##STR1## wherein R, R' and R" eachmay be hydrogen or hydrocarbyl of 1 to about 300 carbon atoms.Hereinafter the terms "Type 1" and "Type 2" will be used to refer toboth the final products or to the alkenylsuccinic anhydrides and thelactone intermediates from which the products are derived.

Normal olefins (R' and R" are hydrogen) and branched olefins (R" ishydrogen) may produce ##STR2## wherein the dangling valence representsthe remainder of R'. In each of these cases at least one of theunsaturated carbon atoms is in the main chain of the alkenyl group andthe carbon atom adjacent to the succinyl group contains two hydrogenatoms. The lactone acetic acid produced from these anhydrides (Type 1)is a gamma-hydrocarbyl-gamma-butyrolactone acetic acid. Controlledreaction with an alkali metal compound or amine leads to the metal oramine, i.e. organoammonium salt of the lactone acid. Heating the aminesalt to remove water would produce amide of the lactone acid. Furtherreaction of the metal or amine salt or amide with an amine produces thecorresponding 3-amidocarbonyl-5-hydroxycarboxylate. The amide of thelactone acid may also be reacted with a metal salt to produce the amideof 3-metallocarboxy-5-hydroxycarboxylate. At least one of R and R' isalkyl containing from 1 to about 30 carbon atoms, and more preferablyone is alkyl of 5 to 25 carbon atoms and the other hydrogen. Thesecarboxylates are excellent hard water soaps, containing metal and amidogroups in the same molecule.

However, higher molecular weight alkenylsuccinic anhydrides derived fromolefin polymers, such as polyisobutylene, may have a number of sidechains as in the following illustrative structure ##STR3## wherein R" ishydrocarbyl. The resulting lactone acetic acids made from suchanhydrides (Type 2) are understood to consist of at least a large, ifnot predominant, portion of beta-hydrocarbyl-gamma-butyrolactone aceticacid. Initial reaction with alkali metal compound or amine produces thecorresponding lactone acid salt or amide. We have found that furtherreaction with amine can be carried out at high temperature, but analysisof the resulting product reveals the presence substantially of thelactam acetate salt or amide. It is noted that commercially availableolefin polymers and the alkenylsuccinic anhydrides obtained therefrommay consist of mixtures which include various types of interlinking.Hence, some ring-opening reaction may occur in the same reactionmixture. It is contemplated, therefore, that some 5-hydroxycarboxylateproducts may be present in the final product mixture.

The various reaction products of this invention will be discussed inmore detail subsequently.

In one aspect of this invention, an alkenylsuccinic anhydride is reactedwith a mineral acid in the presence of water, preferably under refluxconditions. This hydrolytic reaction yields the corresponding lactoneacetic acid and from 40% to 50% by weight of alkenylsuccinic acid. It isunexpectedly discovered that if the reaction mixture is treated with aninert organic solvent, such as toluene, and distilled, the solvent,water and acid may be withdrawn, leaving the lactone acetic acidcomponent untouched, while the alkenylsuccinic acid is converted back tothe alkenylsuccinic anhydride. The anhydride is further treated withacid and water to yield a new reaction mixture containing over 80% ofthe desired lactone acetic acid. A second distillation with solventfollowed by the acid-water treatment produces a reaction mixturecontaining at least 90% by weight of the lactone acetic acid.

Hydrochloric acid and toluene are the preferred acid and solvent in thisreaction sequence because they permit water to be removed convenientlyas an azeotrope with the toluene. Other solvents include benzene, xyleneand the like. A 6-normal hydrochloric acid concentration is preferred. Atypical reaction between hydrochloric acid and succinic anhydride in thepresence of water is understood to proceed as follows: ##STR4## whereinR, R' and R" have the aforesaid definitions.

A modification of this process involves reacting the alkenylsuccinicanhydride with an alcohol or mercaptan in the presence of an acid-actingcatalyst. This process is disclosed and claimed in U.S. application Ser.No. 324,939, filed on Jan. 19, 1973 now U.S. Pat. No. 3,936,472. Theresulting product is an ester or thioester of the lactone acetic acid,##STR5## R_(a) being the organic portion of the alcohol or thiol, of 1to 20 carbon atoms, preferably 1 to 6. This mode of preparation ispreferred because the anhydride is converted to a lactone acid compoundin only one step at 90% or more yield. The ester or thioester may bereacted directly with an amine to produce the lactone amide;alternatively each may be hydrolyzed back to the lactone acid forfurther reaction with the alkali metal compound.

Preferred alcohols in this process are the lower aliphatic monohydricalcohols of from 1 to 6 carbon atoms. Methanol is particularlyconvenient to employ. Also useful are ethanol, propanol, butanol,pentanol, and such thiols as methyl mercaptan, ethyl mercaptan, and thelike. Heterogeneous catalysts useful in this process include thepreferred ion-exchange resins having acid groups attached. Sulfonic acidgroups attached to a vinyl or vinyl-copolymer matrix provide a veryeffective catalyst. Mineral acids, such as hydrochloric, other sulfonicacids, such as p-toluenesulfonic, are also suitable.

TYPE 1 PRODUCTS

The lactone acetic acid or ester or thioester derived from the Type 1alkenylsuccinic anhydride is reacted with an alkali metal compound or anamine which does not open the lactone ring. A strong alkali, such assodium hydroxide, could open the lactone ring. The resulting di-sodiumsoap, while having soap properties, can be precipitated in hard water bycalcium or magnesium. Therefore, one of the preferred Type 1 products ofthis invention is that in which an amine is reacted with the lactoneacid first to produce a lactone amine salt, or a lactone amide. Then astrong alkali, preferably sodium hydroxide or other alkali hydroxides,may then be reacted with the intermediate to open the ring, therebyplacing a metallo-carboxy group at the 3-carbon of the carboxylate, asin ##STR6## wherein the dangling valence is the remainder of the aminereactant and M is the alkali metal. Products of this type possess verygood utility as aqueous detergents.

Also of importance in this invention are those products in which themetal or amine salt or amide is prepared initially, followed by openingthe ring with an amine instead of the metal reactant. The alkali metalcompound is preferred as the initial reactant in this modification. Themost suitable alkali reactants include alkali metal carbonates andbicarbonates, for example sodium bicarbonate, sodium carbonate,potassium bicarbonate, potassium carbonate, lithium carbonate and thelike; also the metal hydrides, such as lithium hydride. The alkali metalneutralizes the acetic acid portion of the molecule without opening thering of the lactone. This reaction may be carried out in the presence ofa polar solvent such as water, mono- and polyhydric alcohols and ethersof from about 1 to 6 carbon atoms, such as methanol, ethanol, propanoland dimethoxyethane, inert hydrocarbons, such as toluene or benzene,also tetrahydrofuran and mixtures thereof. Lithium hydride is preferablyused in tetrahydrofuran. A water-methanol mixture also provides asatisfactory solvent system. The resulting mono-metal salts of thegamma-lactone acid have cleaning properties and form suds in water,although they are also precipitated by calcium.

The amines also useful in this phase of the reaction sequence, includeboth primary and secondary alkyl amines, cycloalkyl amines and aralkylamines, ethylenepolyamines, and alkanolamines and ethoxylated(pre-reacted with ethylene oxide) alkanolamines. The amine reactants mayhave from 1 to about 20 carbon atoms and from 1 to about 10 nitrogenatoms.

The gamma-lactone acetic acid soaps or amides are understood to have thefollowing structure: ##STR7## wherein R and R' may each be hydrogen oralkyl of from 1 to about 30 carbon atoms, and M is an alkali metal, (OX)is the substituted ammonium of the amine reactant and X is the aminogroup --N< of the amine reactant.

These soaps or amides are then reacted with an amine. The lactone ringopens and the carbonyl group of the lactone forms an amide with theamine.

The amines useful in this second step of our invention may be any aminehaving an --NH-- group, such as alkyl, cycloaklyl, aralkyl and the likeof from 1 to about 20 carbon atoms, including methyl amine, ethyl amine,diethyl amine, propyl amine, dipropyl amine, hexyl amine, dodecyl amine,cyclohexyl amine, benzyl amine and polyamines, particularly ethylenepolyamines, such as ethylene diamine, diethylene triamine, triethylenetetramine and tetraethylene pentamine. This second amine may be the sameas that used in the preceding step. Of particular interest are thealkanolamines, such as diethanolamine and monoethanolamine which is themost preferred reactant for preparing aqueous soaps and detergents. Thissecond reaction can be carried out in the presence of any solvent asused in the previous reaction or in a nonpolar solvent depending uponthe reaction temperature desired. The reaction mixture may be refluxedat temperatures ranging from over room temperature, about 30° C., to250° C., preferably up to about 175° C. Reaction with monoethanolaminepermits an equimolar reaction, i.e. 1 mole of amine per mole of metalsalt, or amine salt.

It is understood that Type 1 product of this reaction sequence is a5-hydroxy carboxylate, having the general structure: ##STR8## wherein Mand X have the previous definitions and the dangling valences are theremainder of the amine reactant. One of the most preferred compounds ofType 1 is ##STR9## wherein R is alkyl of 5 to 25 carbon atoms, R' ishydrogen, and M is sodium. The metal hydroxyamides are so effective inhard water that they are not precipitated by the presence of highconcentrations of calcium or magnesium.

The preferred reaction product may be further reacted with ethyleneoxide to produce ethoxylated derivatives. Ether groups are added ontothe ethanolamine portion of the molecule and provide additionalhydrophilic properties to the soap. From 1 to 20 moles of ethylene oxideper mole of hydroxyamide soap may be added. The reaction may be carriedout at low temperatures, using a liquefied ethylene oxide feed. Theethanolamine reactant may also be pre-ethoxylated before reaction withthe metal lactone acid soap.

TYPE 2 PRODUCTS

The second class of products of this invention are useful in organicindustrial fluids, such as lubricating oils, greases, fuels,transmission fluids and the like. The alkenyl portion of the succinicanhydride from which they are derived is obtained from olefin polymers,preferably derived from propylenes, butylenes, amylenes, hexenes and thelike. One or any combination of R, R' and R" may be hydrocarbyl of from25 to 800 carbon atoms. Preferably, the total carbon atom content of thealkenyl group may range from 30 to about 300 carbon atoms, and thedifferent R-groups are alkyl.

As discussed previously, unbranched long-chained hydrocarbon olefinpolymers used in preparing the alkenylsuccinic anhydride precursor arenot readily obtainable, and moreover, they may produce waxy products.High molecular weight olefins suitable for making organic fluidadditives are often branched, such as polyisobutylene. Although thisType 2 alkenylsuccinic anhydride may be converted to the lactone acid orester or thioester (as the Type 1 anhydride), we have found that thelactone ring is not readily opened by subsequent reaction with amines oralkalis to produce the 5-hydroxycarboxylate products of Type 1.

The preferred products of this aspect of our invention are those inwhich the lactone acid or ester is reacted with an amine having at leastone --NH₂ group at a temperature of from 125° to about 300° C., andpreferably from 175° to 275° C., to yield a lactam amide believed tohave the structure ##STR10## wherein R, R' and R" may be hydrogen orhydrocarbyl, R" preferably being alkyl, the total R, R' and R"containing from about 30 to about 800 carbon atoms and the danglingvalences being the remainder of the amine reactant. Different amines maybe used to form the amide group and the lactam group, e.g. a polyaminefor the amide and a monoamine for the lactam ring.

The preferred amine reactant used in preparing dispersants or detergentsfor organic compositions is alkylene polyamine of the formula H₂N--(C_(m) H_(2m) NH)_(n) --H, wherein m is an integer of 2 to 4 and n isan integer of 1 to 10, preferably 1 to 6. Preferably, m is 2, and theamines are ethylene diamine, diethylene triamine, triethylene tetramine,tetraethylene pentamine, pentaethylene hexamine and the like. However,monoamines may be used of from 1 to about 30 carbon atoms, such as thealkyl amines, methyl amine, ethyl amine, butyl amine, cyclohexyl amine,etc., and aralkyl amines, e.g. benzyl amine.

When the preferred polyamines are used, the final reaction product maycontain the above structures and polymers thereof, poly(lactam)amidomolecules having up to over 3,000 carbon atoms. If P stands for thedivalent polyamino group --(C_(m) H_(2m) NH)_(n-1) --C_(m) H_(2m) --, LAstands for a divalent lactam amido ##STR11## and AL stands for adivalent amido lactam ##STR12## then the following products may occur inthe reaction mixtures of this invention: --P--LA--P--AL--,--P--LA--P--LA--, --P--AL--P--LA--, --P--AL--P--AL--,--P--AL--P--LA--P--AL--P--AL--, --P--LA--P--LA--P--AL-- and the like.The lactone amides of polyamines may also interact under the conditionsof this invention to produce bis(lactam)amides. If the same amine isused to form both the amide and the lactam, the addition of amine tolactone acid or ester may be carried out in a single step. Both lactoneand lactam amides are useful in the organic compositions of thisinvention.

The metal lactam acid salts may also be prepared by reacting the lactoneacid with the alkali metal compound, followed by reaction with theamine. Using tetraethylene pentamine as the amine and a sodium salt ofthe lactone acid for illustration, the reaction products may have thestructures ##STR13##

These high molecular weight monomeric and polymeric lactone and lactamproducts and the above salts also have detergent and dispersantproperties in lubricating oils and other organic fluids. The preferredamine for the preparation of high molecular weight bis(lactone)amidesand lactam amides, as indicated above, is tetraethylene pentamine. Thepreferred polyolefin used in the formation of the succinic anhydride ispolyisobutylene or polybutene. Alkaline earth metal salts are alsouseful detergents.

We have further discovered that the lactone and lactam amides can bereacted with a metal salt of an alcohol or phenol and carbon dioxide toform a metal carbamate with any basic nitrogen atom remaining in themolecule. Alkali or alkaline earth metal alkoxides or phenates, such assodium, potassium, calcium, barium and the like salts are suitablereactants. The preferred alcohols contain from 1 to about 20 carbonatoms. Simple alcohols, such as methanol, propanol, butanol, t-butanol,amyl alcohol, hexanol and the like may be used. Phenol or C₁ -to C₂₀-alkylphenol are also satisfactory sources for the metal salt. Ofinterest are the over-based salts in which the metal, preferablyalkaline earth metal, is present in a greater concentration thanstoichiometric. Preparations of such over-based phenates are well known,such as described in U.S. Pat. No. 3,350,310 and U.S. Pat. No.3,036,971. The metal salt and the lactam or lactone amide are mixedtogether in the presence of carbon dioxide under moderate heat or atroom temperature for a sufficient period of time to effect reaction.

It is understood that any terminal or internal nitrogen atom on thepolyamine can enter the carbamate reaction, as for example ##STR14##These carbamates have utility as oil or gasoline dispersants ordetergents.

We have also discovered that the lactone and lactam amide products ofthis invention may form complexes with metal compounds, particularlywith the metals of Groups Ib, IIb or VIII of the Periodic Table, such aszinc. Of particular interest are zinc salts of organic acids andphenates, such as zinc carboxylates of 1 to 20 carbon atoms, zincmethane sulfonate, zinc hydroquinones, and zinc phenates.Alkyl-substituted phenates and hydroquinones may also be used, in whichthe alkyl groups contain from 1 to about 25 carbon atoms. The complexesmay be prepared by adding the zinc salt to the reaction mixturecontaining the lactone or lactam amide or the amide may be blended intothe organic medium, such as a lubricating oil, first and then the zincsalt is added. The amide and salt are heated slightly under agitationuntil solution is obtained.

The following examples are provided for the purpose of illustrating thevarious aspects of this invention.

EXAMPLE 1

A one-liter flask is fitted with a magnetic stirrer and a refluxcondenser, and 153 g of n-hexadecenyl succinic anhydride (0.475 mole)are introduced. To this is added 200 ml of 6 N. hydrochloric acid. Themixture is stirred and brought to reflux. The reaction mixture is heldat reflux for 17 hours. Then 150 ml of toluene are added, and the waterand hydrochloric acid are distilled from the system by means of aDean-Stark trap to convert by-product diacid back to anhydride.Distillation is continued to take off the toluene. The Dean-Stark trapis then removed and the 200 ml of 6 N. hydrochloric acid replaced in theflask. Again the mixture is refluxed with stirring for 17 hours. The 150ml of toluene is added back, and the dilute acid again distilled off.Treatment with 6 N. hydrochloric acid is repeated in this way for twomore times. The toluene is distilled off leaving 161 g. ofgamma-n-tetradecyl-gamma-butyrolactone-2-acetic acid. Infrared spectrashow the purity to be 90%.

EXAMPLE 2

A solution of 50 g of gamma-n-decyl-gamma-butyrolactone-2-acetic acid(0.176 mole) is prepared in a one liter round bottom flask containing500 ml of dry tetrahydrofuran at 25° C. The flask is fitted with astirrer, condenser, and gas inlet tube. To this is added 1.40 g oflithium hydride (0.176 mole) under nitrogen. The mixture is stirred andbrought to reflux. The mixture is heated at reflux for 40 hours. To thisis then added 16.2 g of ethanolamine (0.264 mole) and refluxing undernitrogen is continued for 22 hours. A small amount of white insolublesolid is removed by filtration. The product is recovered from thefiltrate by evaporation of solvent and excess amine by using a bath at90° C. and pressure down to 1 mm Hg in a rotary evaporator. The yield oflithium 3-hydroxyethylamido-5-hydroxypentadecanoate is 52 g.

EXAMPLE 3

A solution of 14.0 g of gamma-n-decyl-gamma-butyrolactone-2-acetic acid(0.0493 mole) is prepared in 200 ml of refluxing methanol in a 500 mlround bottom flask fitted with a condenser. A solution of 4.57 g ofsodium bicarbonate (0.0542 mole) is prepared in a beaker containing 30ml of water at 65° C. The hot bicarbonate solution is poured slowly intothe refluxing solution of lactone-acid in methanol. The mixture isrefluxed for ten minutes after the addition is made. Methanol and waterare then removed in a rotary evaporator. The sodium salt residue isdissolved in 100 ml of refluxing tetrahydrofuran in a 500 ml roundbottom flask, fitted with a reflux condenser, to give a cloudy solution.The heat is turned down to stop refluxing, and to the solution is added3.00 g of ethanolamine (0.0490 mole). The mixture is then reheated toreflux under a nitrogen atmosphere. The reaction mixture is held atreflux for 45 hours. After cooling to room temperature, the solution isfiltered to remove a small amount of white solid. Removal of thetetrahydrofuran from the filtrate by rotary evaporation leaves 15.3 g ofsodium 3-hydroxyethylamido-5-hydroxypentadecanoate.

EXAMPLE 4

By the method of example 3 a monosodium salt is prepared by the reactionof gamma-n-tetradecyl-gamma-butyrolactone-2-acetic acid (16.7 g) withsodium bicarbonate (5.0 g). The crude sodium salt (0.049 mole) is heatedand stirred with 100 ml of tetrahydrofuran. After cooling to 30° C. itis filtered free of suspended white solid. The filtrate is transferredto a 300 ml round bottom flask and solvent is evaporated off to leave 50ml of solution. To the solution of the sodium salt is added 3.00 g ofethanolamine (0.0490 mole). The mixture is then refluxed for 72 hoursunder nitrogen. Removal of the solvent by rotary evaporation gives ayield of 20 g of sodium 3-hydroxyethylamido-5-hydroxynonadecanoate.

EXAMPLE 5

Gamma-n-tetradecyl-gamma-butyrolactone-2-acetic acid (10.0 g) (29.4millimoles) is dissolved in 10 ml of dry tetrahydrofuran in a 200 mlflask by heating and stirring. To this solution are added 4.5 g (73.5millimoles) of ethanolamine. The flask is fitted with a reflux condenserand the mixture is brought to reflux for three hours. Solvent and excessethanolamine are evaporated off at 1 mm of mercury pressure to leave ayield of 13.6 g of 2-hydroxyethylammonium3-hydroxyethylamido-5-hydroxynonadecanoate.

EXAMPLE 6

A solution of 102 g of alkyl-gamma-butyrolactone-2-acetic acid (0.049mole) is prepared in 500 ml of tetrahydrofuran. The acid was obtained byreacting polyisobutylene having a molecular weight of about 900 (about64 carbon atoms) with maleic anhydride and treating the resultingalkenylsuccinic anhydride in a manner similar to Example 1. The solutionis then treated with 1.0 g of lithium hydride (0.124 mole), as inExample 2. After 63 hours at reflux the excess lithium hydride isfiltered off. Removal of the tetrahydrofuran from the filtrate by rotaryevaporation leaves 102 g mixture of lithium beta-alkyl- andgamma-alkyl-gamma-butyrolactone-2-acetate. The lithium salt (50 g,0.0238 mole) is placed in a 200 ml flask along with 2.20 g (0.0119 mole)of tetraethylene pentamine under a reflux condenser. The mixture is heldunder a nitrogen atmosphere and heated at 240° C. with stirring for 18hours. The product is then blown with a stream of nitrogen for 2 hoursat 240° C. to yield 51 g of bis(lithiumbeta-alkyl-gamma-alkyl-gamma-butyrolactam-2-acetate) of tetraethylenepentamine.

EXAMPLE 7

A 200 ml round bottom flask is fitted with a reflux condenser, nitrogeninlet tube, thermometer and magnetic stirrer. There are then introduced30.0 g (0.014 mole) of the lactone acid used in Example 6 and 2.65 g(0.014 mole) of tetraethylene pentamine. The mixture is stirred andheated under nitrogen at 240° C. for 24 hours. The flask is then flushedwith nitrogen for 1 hour, and then cooled to yield 32 g of a reactionmixture containing a polymeric amido-lactam believed to have thestructure ##STR15## R, R', R' together having about 64 carbon atoms, nbeing at least one. Infrared analysis of this product shows a band at1650-1680 cm⁻¹ due to the amide carbonyl group, and a band at 1700 cm⁻¹due to the lactam carbonyl group.

It should be noted that reaction between the lactone acid and an amine(as opposed to the alkali metal compound) would normally produce thesubstituted ammonium salt. However, under high temperature conditions,the amide forms at the acetic acid portion of the molecule. Also, theremay be both simpler as well as more complicated polymeric molecules inthe reaction mixture.

EXAMPLE 8

Into a 5-liter flask fitted with a reflux condenser, stirrer andthermometer were added 1220 grams of a product of a reaction betweenpolyisobutene of about 1300 molecular weight (about 93 carbon atoms) andmaleic anhydride. About 700 grams (0.5 mole) of the added amount is thesuccinic anhydride, the remainder being unreacted polyisobutene. To theflask were added 1200 ml of n-octane with moderate heating (to about 50°C.) and agitation to form a solution, followed by 46 grams (1.5 mole) ofmethanol and 150 grams of an ion exchange resin of sulfonic acid on avinyl-divinylbenzene copolymer matrix in bead form. The mixture washeated to reflux with stirring for 12 hours. The resulting solution wasseparated from the beads and filtered.

Atmospheric distillation of the solution took off 32 grams of methanoland the n-octane. The remaining 1236 grams consists of the 520 grams ofpolyisobutene and about 716 grams of the methyl ester of thecorresponding lactone acetic acid. Infrared spectra shows about 90%gamma-butyrolactone ester and about 10% of a delta-lactone ester.

EXAMPLE 9

Into a 500-ml flask were added 100 g (0.34 mole) ofn-tetradecenylsuccinic anhydride, 16.3 grams (0.51) of methanol and 250ml of n-octane. The reaction mixture was heated to reflux at about 70°C. with stirring. The temperature rose to 80° C. and maintained at thatlevel for two hours. Octane and excess methanol were stripped offleaving 105 grams of the half methyl ester of n-tetradecenylsuccinicacid.

In a sealed glass pressure vessel, containing 47 grams of the said halfester, 15 grams of the sulfonic acid resin catalyst of Example 8, 50 mlof n-octane and 10 drops of methanol, the reaction mixture was stirredand heated at 125° C. for three hours. The mixture was then cooled,diluted with ethanol and the catalyst filtered off. Ethanol and octanewere evaporated leaving 41.6 grams of the methyl ester of thecorresponding lactone acid.

This ester is hydrolyzed with hydrochloric acid and the resultinglactone acid is reacted in the same manner as in Example 4 to producethe sodium 3-hydroxyethylamido-5-hydroxyheptadecanoic acid.

EXAMPLE 10

Into a 4-necked flask fitted with a Dean-Stark trap under a condenser,thermometer, stirrer and nitrogen inlet tube are added 1620 grams of areaction product prepared in a manner similar to that of Example 8, ofwhich about 58% by weight is the methyl ester of thealkyl-gamma-butyrolactone acetic acid (0.648 mole) and the remainder ispolyisobutene, and 122.7 grams (0.648 mole) of tetraethylenepentamine.The reactor is swept with nitrogen and sealed under a nitrogenatmosphere. The contents of the flask are stirred and heated to 140° C.After 4 hours at this temperature, the temperature was raised to 220° C.while methanol was collected in the trap. The mixture was held at thistemperature for 20 hours. The yield of resulting reaction product is1720 grams.

EXAMPLE 11

Using equipment and procedure similar to that of Example 10, a mixturewas prepared consisting of 747 grams of a reaction product (1) preparedin a manner similar to that of Example 8 except that the alkyl groups onthe lactone ring contain about 64 carbon atoms, of which product about81% by weight is the methyl ester of the alkyl-gamma-butyrolactoneacetic acid (0.575 mole) and the remainder is polybutene, and 851 gramsof a reaction product (2) prepared as in Example 8 except the alkylgroups on the lactone ring contain about 190 carbon atoms, of whichproduct about 47.5% by weight is the methyl ester (0.144 mole), to whichmixture were added 136 grams (0.719 mole) of tetraethylenepentamine. Thereaction mixture was heated at 140° C. under nitrogen for 4 hours and at220° C. for 20 hours with stirring. The yield of resulting reactionmixture was 1710 grams.

EXAMPLE 12

Zinc complexes were prepared by mixing the lactam-amide prepared in amanner similar to that of Example 10 into a mineral lubricating oilblend at a concentration of about 5% by weight. The oil blend was heatedto about 60° C. with stirring and the zinc salt was added in sufficientamount to provide a particular concentration of zinc. The salts usedwere (a) monozinc di-(dodecyl)hydroquinone, (b) dizinc2,2'-methylene-bis(6-octadecylhydroquinone) and (c) monozinctri(octadecyl) phenol.

EVALUATION OF PRODUCTS

The lower molecular soaps of this invention are tested in very hardwater in which the water hardness, calculated as parts per million ofcalcium carbonate is 450. The soap is added at a concentration of 0.4%by weight. The products of examples 2 and 3 are tested as well as thesodium soap of a C₁₉ acid (sodium3-hydroxyethylamido-5-hydroxy-nonadecanoate). None of the soaps testedresults in precipitation of calcium. A similar test is carried out usingthe same soap concentration with an ordinary sodium palmitate. Uponmixing, the calcium soap precipitates and no suds are obtained. Sodiumpalmitate soap is mixed with the product of Example 3, theconcentrations being 0.3% by weight of the hydroxyamide soap and 0.2% byweight of sodium palmitate. This mixture is precipitated in the hardwater. However, the precipitate remains dispersed for over 3 hours.

The washing properties and resistance to precipitation in hard water ofthe products of this invention, even in absence of conventional buildersand sequestrants, are demonstrated in a series of washing tests. Thetests are made in a Terg-O-Tometer Model 7243, manufactured by UnitedStates Testing Company, Inc. of Hoboken, N.J., using a test procedureessentially as recommended by United States Testing. Several soaps areused by adding various amounts to a liter of water having a hardness ofat least 100 ppm. as CaCO₃. Soiled cloths with an average reflectance of67% are cleaned by essentially the following procedure: the cloth isplaced in a 2-liter stainless steel beaker with the sample soap solutionat about 120° F. and agitated by an impeller at 110 cycles per minutefor 15 minutes; the cloths are rinsed in the same hard water for from 2to 5 minutes. After drying the cloths are measured for reflectance in areflectance meter which reads percent of reflected light, usingmagnesium oxide as 100% reflectance. The increased reflectances of thecleaned cloths are as follows:

    ______________________________________                                                                   Increased                                          Soap       Conc., % bw     Refl., %                                           ______________________________________                                        FMPA 101 COTTON CLOTHS                                                        Product of                                                                    Example 2  0.02            7                                                             0.04            9.7                                                Product of                                                                    Example 4  0.02            8                                                             0.04            12.8                                               DACRON/COTTON CLOTH                                                           Product of                                                                    Example 4  0.02            8.8                                                           0.04            18.2                                               ______________________________________                                    

Several soaps are tested in this test in the presence of otheradditives, as follows: 15% soap, 5% sodium silicate, 39.5% sodiumtripolyphosphate, 39.5% sodium sulfate and 1% sodium carboxymethylcellulose. The product of example 4 provided an increased reflectancefor Dacron/cotton cloths of 25% and for EMPA 101 cotton of 32%. A sodium3-hydroxyethylamido-5-hydroxy-C₂₁ carboxylate, in this formulation,provided an increased reflectance for Dacron/cotton cloths of 25% andfor EMPA 101 cotton of 31%.

In a simulated washing test, 200 ml of hard water (CaCl₂ at 450 ppmcalculated as CaCO₃) is placed in a rectangular porcelain wash bowl(with plunger drain) of 14 in.×101/2 in.×7 in. deep (at plunger). Then200 ml of H₂ O containing 300 mg of a soap is poured in. The hardness isnow 225 ppm as CaCO₃. The water is gently stirred with a microspatulafor 2 minutes, then allowed to stand for 3 minutes. The plunger israised to permit the water to drain over 1 minute. After another minute,the bowl is wiped dry with a pre-dried tared paper towel.

The paper towels used in this test are first wetted with distilled waterand dried in an oven at 75° C. for 11/2 hours, then weighed and allowedto cool at room temperature for 1 hour. The towels are again weighed.All weighings are done in a tared 250 ml beaker. The moisture in theatmosphere provided an increase in weight of 7 mg.

The soaps used in the test are the product of example 4 and sodiumstearate. If precipitates form in the bowl during mild agitation, theweight of the towel after wiping the bowl would be increased. Thefollowing results are obtained:

    ______________________________________                                        Soap                Weight Gain, mg                                           ______________________________________                                        Blank                7 (atmospheric                                                               moisture)                                                 Example 4 product   11                                                        Sodium Stearate     69                                                        ______________________________________                                    

The following test shows the ability of the high molecular weightlactams of this invention to maintain particulate solids in oils insuspension.

(a) In a stainless steel cylindrical cell mounted in a constanttemperature bath of 100° C., 1 g of nickel powder is formed in a porousbed on a 400-mesh nickel screen, and 5 cc of a white oil is passedthrough to set the powder and fill the spaces of the cell bed. Then, 10cc of the white oil solution containing 2% by weight of a dispersant and250 ppm of carbon black (0.18 micron diameter) dispersed therein ispassed through the bed at 1 cc/min. Light transmission measurements ofthe mineral oil-dispersion are made before and after the passage throughthe bed to determine the amount of dispersed carbon adhering to thenickel bed (Beer-Lambert law is applicable).

(b) A modification of this procedure involves depositing carbon black onthe bed separately by passing 10 cc of a dispersion of 250 ppm of thecarbon black in white oil through the bed at 1 cc/min. followed by 5 ccof white oil alone. Then the white oil-additive solution is passedthrough at 1 cc/min. Again, this solution has been measured before andafter for light transmission. The percent of light transmission isproportional to the amount of carbon present.

Products of Ex. 7 and 10 are compared with a bis-alkenylsuccinimidewherein the alkenyl group has a formula weight of about 900. Thefollowing results are obtained, as percent reduction of carbon black:

    ______________________________________                                                      (a)Deposit    (b)Deposit                                        Dispersant    Avoidancy     Removed                                           ______________________________________                                        None          10             0                                                Alkenylsuccinimide                                                                          50            22                                                Example 7     90            24                                                Example 10    --            45                                                ______________________________________                                    

The higher the percent of carbon black retained or picked up, the moreeffective the dispersant. (Preparation of carbon black dispersions inboth tests involve mixing 12.5 mg of 0.18 micron diameter carbon blackin 50 grams of the detergent solution or white oil alone and subjectingthe mixture to ultrasonic radiation to 80 KC/sec for 15 minutes.)

The zinc complexes of lactam amides as prepared in Example 12 were alsotested in the carbon removal test. The same procedure for preparingthose complexes were used for complexing the abovebis-alkenylsuccinimide for the purpose of comparison, using the samebase oil stock in each comparison. The concentration of thenitrogen-containing material, 5%, was used for the lactam-amide and thesuccinimide. The results were as follows:

    ______________________________________                                                              Zinc Conc.                                                            Zinc    in Oil,    Deposit                                      Detergent, 5% Salt    (% by wt.) Removed, %                                   ______________________________________                                        Example 12 Product                                                                          (a)     0.062      48                                           Succinimide   (a)     0.062      25                                           Example 12 Product                                                                          (b)     0.021      37                                           Succinimide   (b)     0.021      21                                           Example 12 Product                                                                          (c)     0.062      24                                           Succinimide   (c)     0.062      17                                           ______________________________________                                    

EXAMPLE 13

Into a pressure bottle was added a solution consisting of 25 ml of dryt-butyl alcohol and 64 grams (14.08 m-moles) ofbis(gamma-alkyl-butyrolactone) amide of tetraethylene pentamine (7.04m-moles of amine), the alkyl group being derived from a polybutenehaving a molecular weight of about 1300. Into this solution was mixed asolution of sodium t-butoxide in t-butyl alcohol prepared by dissolving0.324 gram (14.08 m-moles) of sodium in 275 ml of t-butyl alcohol withstirring overnight in a closed flask. The pressure bottle containing themixture is flushed with carbon dioxide and pressurized with CO₂ to 20psig.

The reaction mixture was stirred at room temperature for 24 hours. Thet-butyl alcohol was removed, leaving 64.8 grams of thick liquid product.Infrared spectrum shows the product to be a lactone (5.67 microns)-amide(6.0 microns)-carbamate (6.35 microns).

EXAMPLE 14

A solution of 10 grams (4.2 m-moles) of a lactam amide of tetraethylenepentamine (4.2 m-moles of the amine), the alkyl substituent on the ringhaving a molecular weight of 1300, and 50 ml of n-octane was added to apressure bottle. To this solution was added 1.85 grams of overbasedcalcium phenate containing 4.2 m moles of calcium (or 9.1% Ca) in 10 mlof n-octane. The pressure bottle was flushed with carbon dioxide andpressurized to 20 psig with CO₂.

The mixture was stirred at room temperature for 24 hours. The octane wasremoved under vacuum. The remaining product of 12.0 grams was shown byinfrared analysis to be a lactam (5.88 microns)-amide (6.0microns)-carbamate (6.35 microns).

The products of Examples 13 and 14 were evaluated in the carbon removaltest described previously. A 5% solution of carbamate in white oil waspassed through the bed of carbon black (10 cc at 1 cc/min.). The resultsfor each product and the oil alone were as follows:

    ______________________________________                                                            Carbon                                                    Dispersant          Removed, %                                                ______________________________________                                        None                 0                                                        Example 13          16                                                        Example 14          20                                                        ______________________________________                                    

The products of this invention may be used as hard water soaps, oradditives for industrial organic fluids. These soaps are useful bothalone or in the presence of known, conventional soap additives, buildersor perfumes and the like. The low molecular metal or ammonium salts ofthe 3-amido-5-hydroxy carboxylates may be used not only in water, butthey are also useful as detergents or dispersants in organic fluids,such as gasoline, light machine oils and the like. As gasolineadditives, R groups of from 10 to about 30 carbon atoms could be used.The higher molecular weight products, mostly lactone amides, lactamamides, bis-lactams, or interlinked polymeric or macro-molecularproducts find utility as detergents or dispersants in mineral oils.

Having described our invention,

We claim:
 1. A lactam-amide-carbamate product prepared by reacting agamma-butyrolactone acetic acid precursor compound having the structure##STR16## wherein each of R, R' and R" is a radical selected from thegroup consisting of hydrogen and hydrocarbon, the total carbon atomcontent of R, R' and R" being 30 to about 300 and wherein the danglingvalence is attached to a member selected from the group consisting offree --OH, salts thereof, --ORa and --SRa, wherein Ra is alkyl of from 1to about 20 carbon atoms, with an alkylene polyamine of the formula H₂N--(C_(m) H_(2m) NH)_(n) --H, wherein m is an integer of 2 to 4 and n isan integer of 1 to 10, said amine being added to the said lactone acidcompound as the sole reactant, said reaction being conducted at anelevated temperature of from about 175° to about 275° C. for a timeeffective to convert said precursor lactone to bis lactam and polymersthereof, and reacting said lactam product in the presence of carbondioxide with an alkali metal or alkaline earth metal alkoxide, phenateor alkyl-substituted phenate, the alkoxides and alkyl substituentscontaining from 1 to about 20 carbon atoms, thereby forming saidcarbamate product.